Insect pests destroy growing and harvested crops. In the United States, agronomic crops must compete with thousands of those pests. In particular, soil-dwelling Coleoptera such as southern corn rootworm, northern corn rootworm, western corn rootworm and Mexican corn rootworm are especially devastating to crops such as corn.
In spite of the commercial insecticides available today, damage to crops, both growing and harvested, caused by insect pests still occurs. Accordingly, there is ongoing research to create new and more effective insecticidal agents.
Certain N-substituted-2,2,4-trimethyl-3-oxovaleramide compounds are described in Czech. patent number 148,911; Collect. Czech. Chem. Commun., 36(5), pp. 1995-2004 (1971); Journal of Organic Chemistry, 26, pp. 4340-4344 (1961); Journal of Organic Chemistry, 27, pp. 60-64 (1962); and U.S. Pat. No. 3,072,724. However, no insecticidal utility is described for those compounds.
It is, therefore, an object of the present invention to provide compounds which are effective for the control of insect pests.
It is also an object of the present invention to provide a method for the control of insect pests.
It is a further object of this invention to provide a method for the protection of growing and harvested crops from damage caused by insect attack and infestation.
These and other objects of the present invention will become more apparent from the detailed description thereof set forth below.
The present invention comprises substituted anilide compounds which are useful as insecticidal agents. Those compounds are also useful for protecting plants from damage caused by insect attack and infestation.
The insecticidal substituted anilide compounds of the present invention have the structural formula I 
wherein
Y is halogen, C1-C4alkyl, C1-C4haloalkyl, C1-C4alkoxy, C1-C4haloalkoxy, nitro or cyano;
R is hydrogen,
C1-C4alkyl optionally substituted with one C1-C4alkoxy group, or
benzoyl optionally substituted with one or more groups independently selected from halogen, C1-C4alkyl, C1-C4haloalkyl, C1-C4alkoxy, C1-C4haloalkoxy, nitro and cyano groups;
R1 is C1-C4alkyl and R2 is C1-C4alkyl, halogen or hydrogen, or R1 and R2 may be taken together with the carbon atom to which they are attached to form a cyclopropyl ring;
X is 
O or S(O)n;
n is an integer of 0, 1 or 2;
R3 is C3-C6cycloalkyl, or
C1-C6alkyl optionally substituted with one phenyl ring wherein the phenyl ring is optionally substituted with one or more groups independently selected from halogen, C1-C4alkyl, C1-C4haloalkyl, C1-C4alkoxy, C1-C4haloalkoxy, nitro and cyano groups;
R4 is hydrogen, C1-C8alkyl, C1-C8haloalkyl, C1-C6acyl, C1-C6haloacyl, C1-C4alkoxymethyl, C3-C6cycloalkyl, C3-C6alkenyl, C3-C6alkynyl or S(O)nR5; and
R5 is C1-C4alkyl or C1-C4haloalkyl; and the optical isomers, tautomers, agriculturally acceptable salts and agriculturally acceptable metal chelates thereof.
This invention also comprises compositions containing those compounds and methods for using those compounds and compositions. Advantageously, it has been found that the substituted anilide compounds of the present invention, and compositions containing them, are useful for the control of insect pests. The compounds of this invention are also useful for the protection of plants from damage caused by insect attack and infestation.
The present invention provides a method for the control of insect pests which comprises contacting said pests, or their food supply, habitat or breeding grounds with a pesticidally effective amount of a substituted anilide compound of formula I.
The present invention also provides a method for the protection of growing plants from attack or infestation by insect pests which comprises applying to the foliage of the plants, or to the soil or water in which they are growing or are to be grown, a pesticidally effective amount of a substituted anilide compound of formula I.
Insecticidal substituted anilide compounds of the present invention have the structural formula I 
wherein R, R1, R2, R3, X and Y are as described hereinabove for formula I.
Exemplary of halogen hereinabove are fluorine, chlorine, bromine and iodine. The terms xe2x80x9cC1-C4haloalkylxe2x80x9d, xe2x80x9cC1-C8haloalkylxe2x80x9d, xe2x80x9cC1-C4haloalkoxyxe2x80x9d and xe2x80x9cC1-C6haloacylxe2x80x9d are defined as a C1-C4alkyl group, a C1-C8alkyl group, a C1-C4alkoxy group and a C1-C6acyl group substituted with one or more halogen atoms, respectively. Agriculturally acceptable salts of formula I compounds include, but are not limited to, acid addition salts formed from acids such as hydrochloric acid, sulfuric acid and phosphoric acid, and basic salts such as pyridine salts, alkali metal salts and alkaline earth metal salts. In addition, formula I compounds wherein X is 
may form chelates with boron, transition metals such as copper and zinc, and lanthanide metals.
Advantageously, it has been found that the substituted anilide compounds of the present invention are especially useful for the control of soil-dwelling Coleoptera pests such as southern corn rootworms, northern corn rootworms, western corn rootworms, and Mexican corn rootworms.
Preferred formula I compounds of the present invention are those wherein
Y is halogen or C1-C4haloalkyl;
R is hydrogen,
Cl-C4alkyl optionally substituted with one C1-C4alkoxy group, or
benzoyl optionally substituted with one or more groups independently selected from halogen, C1-C4alkyl, C1-C4haloalkyl, C1-C4alkoxy, C1-C4haloalkoxy, nitro and cyano groups;
R1 and R2 are each independently C1-C4alkyl;
X is 
O or S(O)n;
n is an integer of 1 or 2;
R3 is C1-C6alkyl; and
R4 is C6-C8alkyl, C1-C6acyl, C1-C4alkoxymethyl, C3-C6alkenyl or C3-C6alkynyl.
More preferred insecticidal agents of the present invention are those wherein
Y is Cl or trifluoromethyl;
R is hydrogen, C1-C4alkyl, C1-C4alkoxymethyl, or
benzoyl optionally substituted with one or more groups independently selected from halogen,
C1-C4alkyl, C1-C4haloalkyl, C1-C4alkoxy or C1-C4haloalkoxy groups;
R1 and R2 are methyl;
X is 
O or S(O)n;
n is an integer of 1 or 2;
R3 is isopropyl or tert-butyl; and
R4 is C1-C4alkyl, C2-C6acyl, C1-C4alkoxymethyl, allyl or propargyl.
Most preferred substituted anilide compounds of this invention are those wherein
Y is Cl or trifluoromethyl;
R is hydrogen, C1-C4alkyl or C1-C4alkoxymethyl;
R1 and R2 are methyl;
X is 
R3 is isopropyl; and
R4 is C2-C6acyl.
Formula I compounds of this invention which are particularly effective for the control of soil-dwelling Coleoptera pests include
xcex1,xcex1,xcex1-trifluoro-2,2,4-trimethyl-3-oxo-p-valerotoluidide;
xcex1,xcex1,xcex1-trifluoro-2-(isopropylsulfinyl)-2-methyl-p-propionotoluidide;
4xe2x80x2-chloro-3-hydroxy-2,2,4-trimethylvaleranilide, acetate (ester);
xcex1,xcex1,xcex1-trifluoro-N,2,2,4-tetramethyl-3-oxo-p-valerotoluidide; and
N-(ethoxymethyl)-xcex1,xcex1,xcex1-trifluoro-2,2,4-trimethyl-3-oxo-p-valerotoluidide, among others.
Novel substituted anilide compounds of the present invention have the structural formula I 
wherein R, R1, R2, R3, X and Y are as described hereinabove for formula I provided that Y cannot be methyl or methoxy when X is 
R is hydrogen, R1 and R2 are methyl, and R3 is isopropyl.
Formula I compounds wherein X is C(O) may be prepared, as shown in Flow Diagram I, by reacting a substituted aniline of formula II with an acid chloride of formula III in the presence of a base. 
Certain substituted anilide compounds wherein R is other than hydrogen may be prepared, as shown in Flow Diagram II, by reacting a formula I compound wherein R is hydrogen with an electrophile of formula IV in the presence of a base. 
Formula I compounds wherein X is O may be prepared, as shown in Flow Diagram III, by reacting a substituted aniline of formula II with an a-bromoacid halide of formula V in the presence of a base to form an intermediate compound of formula VI, and reacting the intermediate compound with an alcohol of formula VII in the presence of silver oxide. 
Formula I compounds wherein R1 and R2 are taken together to form a cyclopropyl group and X is C(O) may be prepared, as shown in Flow Diagram IV, by reacting a xcex2-ketoester of formula VIII with benzyltriethylammonium chloride, aqueous sodium hydroxide and 1,2-dibromoethane to form an intermediate compound which is acidified with hydrochloric acid to form an acid of formula IX, reacting the formula IX acid with oxalyl chloride to form an acid chloride of formula X, and reacting the acid chloride with a substituted aniline of formula II in the presence of a base. 
Certain substituted anilide compounds wherein X is C(O) and R2 is hydrogen or halogen may be prepared, as shown in Flow Diagram V, by reacting a substituted aniline of formula II with a xcex2-ketoester of formula VIII to form an intermediate compound of formula XI, and reacting the formula XI compound with an alkylhalide of formula XII to form a formula I compound wherein R2 is hydrogen, and optionally reacting the formula I compound wherein R2 is hydrogen with a sulfuryl halide to form a formula I compound wherein R2 is halogen. 
Compounds of formula I wherein R1 and R2 are C1-C4alkyl and X is C(O) may be prepared, as shown in Flow Diagram VI, by reacting a substituted aniline compound of formula II with a lactone of formula XIII. 
Formula I compounds wherein X is CH(OR4) may be prepared, as shown in Flow Diagram VII, by reducing a formula I compound wherein X is C(O) with a conventional reducing agent such as sodium borohydride to form the corresponding formula I compound wherein X is CH(OH), and optionally reacting the formula I compound wherein X is CH(OH) with an electrophile of formula XIV in the presence of a base. 
Certain formula I compounds wherein X is C(xe2x95x90NOR4) may be prepared, as shown in Flow Diagram VIII, by reacting a formula I compound wherein X is C(O) with an optionally substituted hydroxylamine hydrochloride of formula XV in the presence of a base. 
Formula I compounds wherein X is S(O)n may be prepared, as shown in Flow Diagram IX, by reacting a substituted acetic acid of formula XVI with thionyl chloride to form an acid chloride of formula XVII, reacting the acid chloride with a substituted aniline of formula II in the presence of a base to form a formula I compound wherein X is S, and optionally oxidizing the formula I compound wherein X is S with a conventional oxidizing agent to form formula I compounds wherein X is S(O)n and n is 1 or 2. 
Other methods for the preparation of formula I compounds will become apparent from the examples set forth below. In addition, certain compounds of formula I may be converted into other compounds of formula I using conventional procedures known to those skilled in the art.
The substituted anilide compounds of the present invention are particularly useful for the control of Coleoptera pests including, but not limited to, Chrysomelidae such as Diabrotica undecimpunctata (southern corn rootworm), Diabrotica barberi (northern corn rootworm), Diabrotica virgifera (western and Mexican corn rootworms) and Diabrotica balteata (banded cucumber beetle), Elateridae such as Limonius californicus (sugarbeet wireworm), Agriotes mancus (wheat wireworm) and Conoderus falli (potato wireworm), Scarabaeidae such as Popillia japonica (Japanese beetle), and Carabidae such as Stenolophus lecontei (seedcorn beetle). The formula I compounds of this invention are especially useful for the control of soil-dwelling Coleoptera pests such as southern corn rootworm, northern corn rootworm, western corn rootworm, and Mexican corn rootworm.
The formula I compounds of this invention are useful for protecting crop plants and turfgrasses from insect attack and infestation. In particular, the formula I compounds of this invention are useful for protecting corn, potato, sugarbeet, wheat, sugarcane, peanut and soybean crops, and turfgrasses from soil-dwelling Coleoptera attack and infestation. The compounds of this invention are especially useful for protecting corn from southern corn rootworm, northern corn rootworm, western corn rootworm, and Mexican corn rootworm attack and infestation.
The substituted anilide compounds of this invention are effective for controlling insect pests when applied to the foliage of plants and/or to the soil or water in which said plants are growing or are to be grown in sufficient amount to provide a rate of about 0.1 kg/ha to 50 kg/ha, preferably about 0.1 kg/ha to 10 kg/ha, more preferably about 0.5 kg/ha to 2 kg/ha, of active ingredient. The compounds of the present invention are especially useful for protecting crop plants and turfgrasses from soil-dwelling Coleoptera attack and infestation when the compounds are applied to the soil in which the crops and turfgrasses are growing or are to be grown in sufficient amount to provide a rate of about 0.1 kg/ha to 50 kg/ha, preferably about 0.1 kg/ha to 10 kg/ha, of active ingredient.
While the compounds of this invention are effective for controlling insect pests when employed alone, they may also be used in combination with other biological chemicals, including other insecticides. For example, the formula I compounds of this invention may be used effectively in conjunction or combination with pyrethroids, phosphates, carbamates, cyclodienes, endotoxin of Bacillus thuringiensis (Bt), formamidines, phenol tin compounds, chlorinated hydrocarbons, benzoylphenyl ureas, pyrroles and the like.
The compounds of this invention may be formulated as emulsifiable concentrates, flowable concentrates or wettable powders which are diluted with water or other suitable polar solvent, generally in situ, and then applied as a dilute spray. Said compounds may also be formulated in dry compacted granules, granular formulations, dusts, dust concentrates, suspension concentrates, microemulsions and the like all of which lend themselves to seed, soil, water and/or foliage applications to provide the requisite plant protection. Such formulations or compositions of the present invention include a compound of the invention (or combinations thereof) admixed with one or more agronomically acceptable inert, solid or liquid carriers. Those compositions contain a pesticidally effective amount of said compound or compounds, which may vary depending upon the particular compound, target pest, and method of use. Those skilled in the art can readily determine what is a pesticidally effective amount without undue experimentation.